Hydrogen peroxide formulations in barrier layer films with a metallized layer

ABSTRACT

The present disclosure concerns a cosmetic product for modifying the natural color of keratinous fibers, in particular human hair, comprising at least one packaging (VP) and a cosmetic composition (KM) contained in this packaging (VP). The packaging is made of a multi-layer film (F) comprising at least two polymer layers (P1) and (P2) and at least one barrier layer (BS). The cosmetic composition comprises at least one oxidizing agent and at least one thickening agent from the xanthane group. The use of the packaging (VP) in combination with the cosmetic composition (KM) does surprisingly not lead to an inflation of the packaging or an excessive water loss of the agent (KM) during storage.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. § 371based on International Application No. PCT/EP2018/079795, filed Oct. 31,2018, which was published under PCT Article 21(2) and which claimspriority to German Application No. 10 2017 223 040.1, filed Dec. 18,2017, which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The present disclosure is in the field of cosmetics and relates to aproduct for oxidative color change of keratinous fibers, in particularhuman hair, comprising an oxidant-containing composition packaged in apackaging. The oxidizing agent-containing composition comprises athickening agent from the group of xanthanes. The packaging ismanufactured from a special multi-layer film composite system, the wallof which comprises at least two polymeric layers and a barrier layer.The barrier layer has a permeation barrier effect for gases and watervapor. The barrier layer comprises a metal.

BACKGROUND

Changing the color of keratinous fibers, especially hair, is animportant area of modern cosmetics. The appearance of the hair may beadapted to current fashion trends as well as to the individual wishes ofeach person. The expert knows various methods for changing the color ofhair. The hair color may be changed temporarily by using direct dyes. Inthis process, already formed dyes diffuse from the dye into the hairfiber. Dyeing with direct dyes is associated with a low level of hairdamage, but a disadvantage is the low durability and the fastwashability of the colorations obtained with direct dyes.

If the consumer desires a long-lasting color result or a color shadethat is lighter than the original hair color, oxidative color modifiersare usually used. For permanent, intensive colorations withcorresponding fastness properties, so-called oxidative colorants areused. Such dyes usually contain oxidative colorant precursors, so-calleddeveloper components and coupler components, which form the actual dyesunder the influence of oxidants—usually hydrogen peroxides. Oxidativecolorants are exemplified by excellent, long-lasting dyeing results.

Oxidative color modifiers are usually marketed in the form oftwo-component agents, in which two different compositions are separatelypackaged in two separate packages and are not mixed together untilshortly before use. The first composition is a formulation—usuallyacidic for stability reasons—which contains, for example, hydrogenperoxide in concentrations of from about 1.5 to about 12% by weight asan oxidizing agent. The oxidizing agent formulation is usually in theform of an emulsion or dispersion and is usually provided in a plasticbottle with a resealable outlet opening (developer bottle).

This oxidizing agent formulation is mixed with a second compositionbefore use. This second composition is an alkaline formulation which isoften in the form of a cream or a gel and which, if a color change isdesired at the same time as the brightening, also contains at least oneoxidative colorant precursor. This second composition may, for example,be provided in the form of a tube or in the form of a plastic or glasscontainer.

In the usual application form described above, the second composition,which contains the alkalizing agent and/or the oxidative colorantprecursors, is transferred from the tube or container into the developerbottle and then mixed by shaking with the hydrogen peroxide compositionalready in the developer bottle. In this way, the application mixture isprepared in the developer bottle. Application to the hair is thencarried out via a small spout or outlet opening at the top of thedeveloper bottle. The spout or outlet opening is opened after shakingand the application mixture may be removed by pressing the flexibledeveloper bottle.

The use of the developer bottle requires a certain routine from theuser, so that some users prefer to prepare the application mixture in amixing bowl and apply it with a brush.

When preparing the application mixture in a bowl, both components—thefirst composition containing the oxidizing agent and the secondcomposition containing an alkalizing agent and/or oxidative colorantprecursors—are completely transferred into a bowl or similar vessel andstirred there, for example with the aid of a brush. The applicationmixture is then removed from the mixing bowl using the brush. With thisform of application, the use of a voluminous and expensive developerbottle is not necessary, and the search continues for inexpensive andmaterial-saving packaging forms for the oxidizing agent composition.

In this context, packages in pocket or bag form, which are usually madeof plastic films or metal foils, are an inexpensive form of packagingwith low material consumption.

Such packaging may be produced, for example, by gluing or hot pressingtwo plastic foils lying one on top of the other, with the gluing takingplace on all edges of the foils. The interior of the packaging (i.e. theplastic bag) created by the bonding may then be filled with the desiredcosmetic composition. The packaging may be opened by tearing or cuttingopen the plastic bag.

However, filling oxidizing agent compositions into such packaging isassociated with problems caused by the reactivity of the oxidizingagent. Oxidizing agents are highly reactive substances which—dependingon the storage conditions and the presence of decomposingimpurities—decompose in small amounts and produce oxygen (i.e. gas).

The developer bottles known from the state of the art are usually onlyfilled with the oxidizing agent composition to a maximum of half,usually only to a third of their internal volume. As a rule, developerbottles are made of polyethylene. Since polyethylene is permeable toboth water vapor and other gases, there is no or only very slight excesspressure in the developer bottle. In addition, developer bottles areusually provided with strong, thick walls and a sturdy screw cap, sothat the diffusion of water vapor or gases through the thickness of thewalls is reduced and a slight increase in pressure within the bottle hasno negative effects.

In contrast, bag-shaped packages are usually completely filled with theliquid composition, and there is practically no excess air space in thefilled bag. In addition, such packages should be flexible, and whenopened (e.g. torn open or cut open) there should be no uncontrolledescape of the composition. For this reason, when packaging liquidcompositions, the creation of excess pressure in the package should beavoided if possible.

If an oxidizing agent composition is in such packaging, the gas (oxygen)produced during storage may cause the packaging to expand. Since theedges of the package are usually only glued together, in the worst case,strong inflation may lead to bursting of the packaging. For thesereasons, when storing oxidizing agent-containing compositions, thechoice of the film material of which the packaging is made is of greatimportance.

Packages made of pure plastic such as polyethylene or polypropylene arepermeable to both water vapor and gases. When storing a compositioncontaining oxidizing agents in a polyethylene or polypropylene package,the package does not expand. Due to the high permeability of thecomparatively thin film of the packaging to water vapor, however, thewater content of the composition is reduced. If the composition isstored in the packaging for several weeks or months, the water lossexceeds the maximum value permitted for adequate storage stability.

The production of suitable packaging for formulations containinghydrogen peroxide is a challenge. The above mentioned properties for thepermeability of oxygen and water vapor have to be adjusted in such a waythat a sufficient storage stability is given. The layer thickness of thefilm should be kept as low as possible for environmental reasons and topreserve resources. Furthermore, the layer thickness naturally also hasan influence on the manufacturing costs. Against this background, thinlayers are desired, but these do not always guarantee sufficientmechanical strength. If different materials are combined in amulti-layer film in order to satisfy a wide range of requirements, themanufactureability of the multi-layer film must also be guaranteed.Certain materials cannot be combined with each other because thecohesion between layers is not always sufficient or because theirprocessing temperatures may be so different that joint processing isdifficult.

Finally, the film materials are of great importance, especially whenstoring a multi-component system, as substances from the multi-componentsystem can diffuse into the films and promote the detachment of layersforming the film. The choice of components of a hydrogenperoxide-containing formulation therefore also has an impact on thechoice of packaging.

BRIEF SUMMARY

The instant disclosure provides a cosmetic product for modifying thenatural color of keratinous fibers comprising

-   -   (i) at least one packaging comprising at least one multi-layer        film comprising at least one first polymer layer, at least one        second polymer layer and at least one barrier layer, and    -   (ii) at least one cosmetic composition packaged and included in        the packaging:        -   a) at least one oxidizing compound and        -   b) at least one thickening agent, selected from the group of            xanthanes,        -   wherein the first polymer layer is formed of polyethylene            terephthalate or polyethylene naphthalate; the second            polymer layer is formed of a polyolefin; and the barrier            layer is formed of metallized oriented polypropylene.

The objective of the present application was to package hydrogenperoxide-containing formulations in such a way that the mechanicalstrength of the packaging is sufficiently high to allow safe storage,but that easy access to the ingredients is guaranteed.

Surprisingly, it has now been found that oxidizing agent-containingcompositions may be packaged where the water vapor permeability is lowand inflation may be reduced by allowing the film to have a certainlevel of oxygen permeability. The films include a special film compositesystem and also have a barrier layer. By reducing the water vaporpermeability, but adjusting the oxygen permeability to a sufficientlyhigh level, the tendency to expand due to oxygen, which is formed fromthe hydrogen peroxide, is reduced and the mechanical strength isincreased over time.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and isnot intended to limit the disclosure or the application and uses of thesubject matter as described herein. Furthermore, there is no intentionto be bound by any theory presented in the preceding background or thefollowing detailed description.

The subject-matter of the present disclosure is a cosmetic product formodifying the natural color of keratinous fibers, in particular humanhair, comprising

-   -   (i) at least one packaging (VP) comprising at least one        multi-layer film (F) comprising at least one first polymer layer        (P1), at least one second polymer layer (P2) and at least one        barrier layer (BS), and    -   (ii) at least one cosmetic composition (KM) packaged and        contained in the packaging (VP):    -   a) at least one oxidizing compound and    -   b) at least one thickening agent selected from the group of        xanthanes,    -   wherein the first polymer layer (P1) is formed of polyethylene        terephthalate or polyethylene naphthalate, in particular        polyethylene terephthalate, the second polymer layer (P2) is        formed of a polyolefin, in particular polyethylene, and the        barrier layer (BS) is formed of metallized oriented        polypropylene.

Keratinous fibers, keratin-containing fibers or keratin fibers are furs,wool, feathers and in particular human hair. Although the products ascontemplated herein are primarily suitable for lightening and dyeingkeratinous fibers, there is nothing in principle to prevent their use inother areas.

The product as contemplated herein is a product for the oxidative colorchange of keratinous fibers, i.e. a product which is applied on thehuman head in order to achieve an oxidative coloring, a lightening, ableaching or a color nuance of the hair. In this context, color nuanceis understood to be a coloring in which the color result is lighter thanthe original hair color. That the product is to be used “to change thenatural color” means that the product either comprises only an oxidizingagent for bleaching, or that the product comprises an oxidizing agentused with a coupler that is not part of the present disclosure toachieve a color change, or that the product is used with a dye that isnot part of the present disclosure for further hair coloring.

Furthermore, the term “packaging” is understood to mean, as contemplatedherein, a packaging which is preferably in the form of a sachet. Asachet is a small package in the form of a bag or pouch, which is oftenused in the packaging of cosmetics. The capacity of the packaging, inparticular of the sachet, may, for example, be from about 5 to about1000 ml, preferably from about 10 to about 200 ml and particularlypreferably from about 20 to about

In addition, a multi-layer film (F) in the context of the presentdisclosure is understood to be a thin, flat and windable strip includingthe at least one polymer layer (P1) and the at least one polymer layer(P2). This multi-layer film (F) forms the wall of the packaging (VP).The packaging also comprises a barrier layer (BS), which selectivelypermits or reduces the passage of water vapor and other gases such asoxygen.

Furthermore, in the context of the present disclosure, the term“thickening agent” is to be understood as meaning compounds which canbind liquids, in particular water, and increase the viscosity of theseliquids. In the context of the present disclosure, this also includesgelling agents which are capable of thickening liquids into compositionswith a gel-like consistency or into gels. As contemplated herein,gel-like cosmetic products or gels are dimensionally stable, easilydeformable disperse systems including at least two components, thegelling agent (usually a solid, colloidal substance with long orstrongly branched compounds) and a liquid (usually water) as dispersant.The gelling agent forms a spatial network in the liquid, whereby theindividual gel-forming compounds adhere to one another at differentspatial points by major and/or minor valences.

As contemplated herein, the permeability values of the film (F) areadvantageously adjusted. The film (F) thus imparts advantageous barrierproperties to the packaging, especially with respect to the permeabilityfor water vapor: Water Vapor Transmission Rate (WVTR) measured in theunit g/(m² d) or g/(m²24 h) measured according to the ASTM F 1249 methodat about 38° C. ambient temperature and about 100% relative humidity,and for oxygen Oxygen Transmission Rate (OTR), measured in cm³/(m² dbar) or cm³/(m²24 h), where cm³ is equal to cc, at an atmosphericpressure of 1 bar measured according to ASTM D 3985 at about 23° C.ambient temperature and about 50% relative humidity.

The term “xanthanes” refers to polysaccharides which, as contemplatedherein, occur naturally and may be obtained from sugar-containingsubstrates with the aid of bacteria of the genus Xanthomonas.Preferably, xanthane used as contemplated herein contains d-glucose,d-mannose, d-glucuronic acid, acetate and pyruvate in a molar ratio ofabout 28:30:20:17:5.1-6.3, the main chain including β-1,4-bonded glucoseunits (also called cellulose chain). The xanthanes which areparticularly preferred in the context of the present disclosure have theCAS No. 11138-66-2 and the following structural formula:

The cosmetic product as contemplated herein comprises as first componenta packaging (VP) comprising at least one multi-layer film (F). This filmcomprises at least one first polymer layer (P1), at least one secondpolymer layer (P2) and at least one barrier layer (BS). This multi-layerfilm forms the wall or outer shell of the packaging. As described above,such packaging is usually made by gluing, pressing or welding two piecesof film on top of each other (the packaging (VP) is filled with thecosmetic composition (KM) at the same time). i.e. such packaging isclosed at all edges. This packaging may be opened, for example, bytearing or cutting it open.

The thickness of the multi-layer film (F) determines the mechanicalproperties and the strength of the films. It should be designed in sucha way that there is sufficient mechanical stability, but at the sametime the film (F)—and thus the packaging (VP) produced from thefilm—should be flexible enough to allow complete removal of the cosmeticcomposition (KM) from the opened packaging (VP) by pressing orsqueezing. A film meets these requirements if the film (F) has a certaintotal thickness. Preferred embodiments of the present disclosure includeat least one multi-layer film having a total thickness of from about 28μm to about 220 μm, preferably of from about 52 μm to about 180 μm, morepreferably of from about 80 μm to about 140 μm. For the purposes of thepresent disclosure, the total thickness of the film (F) is understood tobe the sum of the thicknesses of all individual layers that the film (F)includes.

The configuration of layers (P1), (P2) and (BS) within the multi-layerfilm (F) may be different. Furthermore, it is also possible that thefilm (F) includes further layers in addition to the layers mentionedabove. In addition, as contemplated herein, it is advantageous if allthe previously mentioned layers are oriented parallel to the surfaces ofthe film (F), i.e. all layers have the same orientation. If themulti-layer film (F) contains the three layers (P1), (P2) and (BS)described above, the following layouts of the layers would be possible(viewed from the interior (in contact with the cosmetic composition(KM)) to the exterior):

-   -   a) *Interior*-Layer (P1)-Layer (P2)-Barrier layer        (BS)-*Exterior*,    -   b) *Interior*-Layer (P1)-Barrier layer (BS)-Layer        (P2)-*Exterior*,    -   c) *Interior*-Layer (P2)-Layer (P1)-Barrier layer        (BS)-*Exterior*,    -   d) *Interior*-Layer (P2)-Barrier layer (BS)-Layer        (P1)-*Exterior*,    -   e) *Interior*-Barrier layer (BS)-Layer (P1)-Layer        (P2)-*Exterior*,    -   f) *Interior*-Barrier layer (BS)-Layer (P2)-Layer        (P1)-*Exterior*.

However, as contemplated herein, it is preferred when the barrier layer(BS) is located between the first polymer layer (P1) and the secondpolymer layer (P2), the second polymer layer (P2) being located on theexterior of the package. In this case, the multi-layer film (F) iscomposed of three layers, layer (P1) being at the innermost and incontact with the cosmetic composition (KM). Layer (P1) is in contactwith the barrier layer (BS), and the barrier layer (BS) is in contactwith layer (P2). In this layer, the layers (P1) and (P2) are notadjacent to each other but are separated by the barrier layer (BS). Theparticular advantage of this configuration is that the—often verythin—barrier layer (BS) is not located on either the inner or outersurface of the multi-layer film (F), but is protected by the polymericlayer (P1) towards the inside and by the polymeric layer (P2) towardsthe outside. In this way, mechanical abrasion or destruction of thebarrier layer (BS) may be avoided as far as possible. It is thereforeadvantageous in the context of the present disclosure if the at leastone multi-layer film (F) contains the at least one barrier layer (BS)between the at least one first polymer layer (P1) and the at least onesecond polymer layer (P2). The use of such packaging has been shown tobe particularly advantageous in terms of increased storage stability, asthis layout avoids mechanical abrasion or destruction of the barrierlayer (BS) as much as possible. In a further preferred embodiment, thebarrier layer (BS) is also located between the two polymer layers P1 andP2, but the first polymer layer (P1) is located on the exterior of thepackage.

As contemplated herein, the exterior of the packaging (VP) is understoodto be that side of the packaging which does not come into contact withthe cosmetic composition (KM) but with the environment. The use of suchpackaging has proven to be particularly advantageous in terms ofincreased storage stability, as this layout shows neither swelling nordelamination during prolonged contact with an oxidizing agent-containingcomposition.

The first polymeric material of the first layer (P1) is, as contemplatedherein, a polyester. This material may be a layer of one polymer type ora layer of a polymer blend. According to the present disclosure, the atleast one first polymer layer (P1) is formed from polyethyleneterephthalate or polyethylene naphthalate, in particular frompolyethylene terephthalate. As contemplated herein, the term “formed” isunderstood to mean that the polymer layer contains at least about 70% byweight, preferably at least about 80% by weight, more preferably atleast about 90% by weight, most preferably at least about 99% by weight,in each case based on the total weight of the polymer layer (P1), of theabove-mentioned compounds.

Polyethylene terephthalate (PET) is a polymer from the polyester group.Polyethylene terephthalate may be produced, for example, bytransesterification of dimethyl terephthalate with ethylene glycol athigher temperatures. In this transesterification reaction, methanol issplit off, which is removed by distillation. The resultingbis(2-hydroxyethyl)-terephthalate is converted to PET bypolycondensation, again producing ethylene glycol. Another method ofproducing polyethylene terephthalate is the direct polycondensation ofethylene glycol and terephthalic acid at high temperatures withdistillation of the resulting water. Polyethylene terephthalate isexemplified by a particularly high mechanical strength. If the PET layerforms the outer layer, this also offers the advantage that the layersunderneath may be printed without the print being rubbed off. The PETlayer is transparent and provides a mechanical protective layer for theprinted layer.

According to a preferred embodiment of the present disclosure, the layerthickness of the first polymer layer (P1) is from about 4 μm to about 50μm, preferably from about 5 μm to about 35 μm, more preferably fromabout 6 μm to about 20 μm. The layer thickness of the PET layer usedaccording to the preferred embodiment of the present disclosure isassociated with special advantages, which are related to generalproperties of PET. PET is exemplified by high dimensionalstability/stiffness. If PET with these layer thicknesses is chosen asthe first polymer layer (P1), this offers an advantageous mechanicaldimensional stability for the film. At the same time, the overallthickness of the film may be kept low, so that a material andresource-saving film may be provided.

Furthermore, the multi-layer film (F) from which the package is madecomprises a second polymer layer (P2) of a second polymeric material.The second polymeric material may be a layer of one type of polymer or alayer of a polymer mixture. It is provided in the context of the presentdisclosure that the at least one second polymer layer (P2) is formed ofa polyolefin, in particular of polyethylene. As contemplated herein, theterm “formed” is understood to mean that the polymer layer comprises atleast about 70% by weight, preferably at least about 80% by weight, morepreferably at least about 90% by weight, in particular at least about99% by weight, each relative to the total weight of the polymer layer(P2) of the aforementioned compounds.

The second polymeric material of the second layer (P2) of themulti-layer film (F) is a polyolefin, in particular polyethylene.Polyolefins are polymers which are produced from alkenes such asethylene, propylene, 1-butene or isobutene by chain polymerization.Polyolefins are saturated hydrocarbons. They are semi-crystallinethermoplastics which are easy to process. They are exemplified by goodchemical resistance. Polyethylene and polypropylene are widely used infilm applications. As contemplated herein, polypropylene is thereforeused for the second layer (P2), but polyethylene is preferred.Polyethylene is produced by polymerization of ethylene using variouscatalysts. For example, polyethylene may be produced by polymerizingethylene in the gas phase or in suspension. The average relative molarmass may be controlled, for example, by adjusting a certain hydrogenpartial pressure during the polymerization of ethylene. Polyethylene maybe processed by extrusion and stretch blow molding, or by pressing,calendering, thermoforming and cold forming.

The second polymer layer (P2) serves as a supporting layer. Althoughpolyethylene has the disadvantage of being permeable to oxygen and watervapor, it has the advantage of being inexpensive and, due to its lowmelting point—lower than that of polypropylene—it is easy andenergy-saving to process.

According to a preferred embodiment of the present disclosure, thesecond polymer layer (P2) has a certain layer thickness. According tothe preferred embodiment of the present disclosure, the second polymerlayer (P2) has a layer thickness of from about 20 μm to about 150 μm,preferably of from about 30 μm to about 110 μm, more preferably of fromabout 40 μm to about 90 μm. In particular, the second polymer layer (P2)has a higher layer thickness than the first polymer layer (P1).

The polymer layers (P1) and (P2) of the multi-layer film (F) compriseorganic polymeric materials, which generally have only an insufficientbarrier effect against gases and water vapor. If the oxidizingagent-containing composition (KM) is packaged in a packaging (VP) madeof a multi-layer film (F), which only comprises the two organic polymerlayers (P1) and (P2), water vapor may escape unhindered, so that thewater content in the composition (KM) changes in an unacceptable wayduring longer storage. To minimize the uncontrolled escape of watervapor from the packaging (VP), the organic polymer layers (P1) and (P2)are therefore used in combination with a barrier layer (BS).

The barrier layer (BS) has a passage barrier effect for gases and watervapor. As contemplated herein, this means that the barrier layer (BS)reduces and controls the permeation rate of water vapor and gasesthrough the film. A film (F) as contemplated herein, which has a barrierlayer (BS) in addition to the layers (P1) and (P2), thus has a reducedwater vapor permeability and a reduced gas permeability compared to acomparable film (with the same overall thickness), which only has thetwo layers (P1) and (P2) but no barrier layer (BS).

For example, the barrier layer (BS) is a thin layer comprising aninorganic material, which may be applied to organic polymer layers usingvapor deposition techniques (e.g. PVD “physical vapor deposition” or CVD“chemical vapor deposition”).

If the barrier layer (BS) is a layer comprising at least one inorganicmaterial, then the films may be made of metals, semi-metals or metal orsemi-metal oxides, for example aluminum, aluminum oxides, magnesium,magnesium oxides, silicon, silicon oxides, titanium, titanium oxides,tin, tin oxides, zirconium, zirconium oxide and/or carbon.

As contemplated herein, the barrier layer (BS) is made of metallized,oriented polypropylene. Polypropylene is alternatively also known aspoly(l-methylethylene), and is a thermoplastic polymer belonging to thegroup of polyolefins. Polypropylene is produced by polymerization ofpropylene (propene) using various catalysts. For example, polypropylenecan be produced by stereospecific polymerization of propylene in the gasphase or in suspension according to Giulio Natta. Polypropylene ascontemplated herein may be isotactic and thus highly crystalline, butalso syndiotactic or amporphous. The average relative molar mass may becontrolled, for example, by adjusting a certain hydrogen partialpressure during the polymerization of the propene. For example,polypropylene may have average relative molar masses of approx. 150,000to about 1,500,000 g/mol. Polypropylene may be processed by extrusionand stretch blow molding, or by pressing, calendering, thermoforming andcold forming.

An oriented polypropylene is defined by the expert as a polypropylenefilm which is stretched during production after an extrusion orcalendering step, namely stretched in the direction of extrusion and/orstretched at about 90° to the direction of extrusion. The film ispreferably stretched in both directions, i.e. films in which the barrierlayer—or the entire film—is biaxially stretched, particularly preferablysimultaneously biaxially. During the stretching step the polymericmaterial is oriented. This is of great importance for the properties ofthe film layer, especially in the case of polypropylenes, since theorientation step determines the shape of the crystalline domains of thepolymeric material and thus the physical properties of the film.

The polypropylene film is metallized. Possible metals are the abovementioned metals aluminum, magnesium, silicon, titanium, tin, andzirconium, especially aluminum. The metals are evaporated onto thecarrier film. According to a preferred embodiment of the presentdisclosure, the ratio of the layer thickness of metal to orientedpolypropylene is from about 1:1000 to about 1:10, preferably from about1:500 to about 1:50, more preferably from about 1:200 to about 1:100.

The production of films with barrier layers comprising inorganicmaterial is known. Also the multi-layer film (F) used in accordance withthe present disclosure may be manufactured by a process which is usedfor the manufacture of known films with barrier layers in the state ofthe art, as described for example in the documents EP 1036813 A1, EP2371539 A1 and EP 1541340 A1.

The barrier layer (BS) may additionally include a thin layer ofinorganic-organic hybrid polymers. These polymers are known in theliterature under the technical term ORMOCER polymers. A typical ORMOCERpolymer may be produced, for example, by hydrolytic polycondensation ofan organo-functional silane with an aluminum compound and possibly withan inorganic oxide component. Corresponding syntheses are disclosed inEP 0792846 B 1, which is referred to in full here. Inorganic-organichybrid polymers (ORMOCER polymers) have both inorganic and organicnetwork structures. The inorganic silicate network structure may beformed in the sol-gel process by controlled hydrolysis and condensationof alkoxysilanes. The silicate network may be specifically modified byincluding metal alkoxides in the sol-gel process. By polymerization oforgano-functional groups, which are introduced into the material by theorganoalkoxylanes, an additional organic network is built up. TheORMOCER polymers produced in this way may be applied to layers (P1)and/or (P2) using conventional application techniques (spraying,brushing, etc.).

The thicker the barrier layer (BS), the greater or stronger the barriereffect against the passage of gases and water vapor. The thickness ofthe barrier layer (BS) may therefore be selected depending on thedesired barrier effect. According to a preferred embodiment of thepresent disclosure, the at least one barrier layer (BS) has a layerthickness of from about 4 μm to about 25 μm, preferably of from about 5μm to about 20 μm, more preferably of from about 6 μm to about 18 μm.

The material, structure and layer thicknesses determine the permeabilityvalues of the film. The multi-layer film (F) of the packaging of thecosmetic product as contemplated herein is exemplified by advantageousproperties with regard to oxygen permeability and water vaporpermeability. The multi-layer film exhibits an oxygen transmission rate(OTR) at about 23° C. and about 50% relative humidity of from about 0.1to about 5 cc/m²/d/bar, preferably from about 0.2 to about 3.5cc/m²/d/bar, more preferably from about 0.5 to about 2.5 cc/m²/d/bar,and a water vapor transmission rate at about 38° C. and about 100%relative humidity of from about 0.1 to about 5 g/m² d, preferably fromabout 0.2 to about 3.5 g/m² d, more preferably from about 0.5 to about2.5 g/m² d.

As contemplated herein, the permeability values of the film (F) areadvantageously adjusted. The film (F) thus imparts advantageous barrierproperties to the package, especially with regard to the permeabilityfor water vapor: Water Vapor Transmission Rate (WVTR) measured in theunit g/(m² d) or g/(m²24 h) measured according to the ASTM F 1249 methodat about 38° C. ambient temperature and about 100% relative humidity,and for oxygen: Oxygen Transmission Rate (OTR) measured in cm³/(m² dbar) or cm³/(m²24 h), where cm³ is equal to cc, at an atmosphericpressure of about 1 bar measured according to ASTM D 3985 at about 23°C. ambient temperature and about 50% relative humidity.

In addition to the layers (P1), (P2) and (BS) described so far, themulti-layer film (F) may additionally comprise one or more furtherlayers. These additional layers may, for example, be intermediate layersand/or adhesive layers. It is therefore preferred as contemplated hereinif the at least one multi-layer film (F) additionally contains at leastone further layer selected from the group of intermediate layers (SZ),adhesive layers (SK) and mixtures thereof.

For example, the films (F) may have further intermediate layers (SZ) toincrease the mechanical stability. Intermediate layers may also preventor minimize the permeation of polymers or remaining monomers from apolymer layer into the cosmetic composition (KM).

To increase bond strength, the films may also comprise one or moreadhesive layers (SK) to reduce or prevent delamination (i.e. peeling orformation of an air space) between two layers.

A particularly preferred product as contemplated herein is themulti-layer film (F) comprises, in addition to the first polymer layer(P1), the second polymer layer (P2) and the barrier layer (BS), one ormore further layers selected from intermediate layers (SZ) and/oradhesive layers (SK).

If the multi-layer film (F) contains other layers in addition to thelayers (P1), (P2) and (BS), the following layouts of the layers arepossible (from interior (in contact with the cosmetic composition (KM))to exterior):

-   -   a) *Interior*-Layer (P1)-First adhesive layer (SK1)-Layer        (P2)-Second adhesive layer (SK2)-Barrier layer (BS)-*Exterior*,    -   b) *Interior*-Layer (P1)-Adhesive layer (SK1)-Layer (P2)-Barrier        layer (BS)-*Exterior*,    -   c) *Interior*-Layer (P1)-Layer (P2)-Second adhesive layer        (SK2)-Barrier layer (BS)-*Exterior*,    -   d) *Interior*-Barrier layer (BS)-First adhesive layer        (SK1)-Layer (P1)-Second adhesive layer (SK2)-Layer        (P2)-*Exterior*,    -   e) *Interior*-Barrier layer (BS)-Adhesive layer (SK)-Layer        (P1)-Layer (P2)-*Exterior*,    -   f) *Interior*-Barrier layer (BS)-Layer (S1)-Adhesive layer        (SK)-Layer (P2)-*Exterior*,    -   g) *Interior*-Layer (P1)-First adhesive layer (SK1)-Barrier        layer (BS)-Second adhesive layer (SK2)-Layer (P2)-*Exterior*,    -   h) *Interior*-Layer (P1)-Adhesive layer (SK)-Barrier layer        (BS)-Layer (P2)-*Exterior*,    -   i) *Interior*-Layer (P1)-Barriere Layer (BS)-Adhesive layer        (SK)-Layer (P2)-*Exterior*

In any case, the film should be designed so that there is sufficientadhesion between the films. According to a preferred embodiment of thepresent disclosure, the bond strength of the film is from about 0.1 toabout 10 N/15mm, preferably from about 1 to about 8 N/15mm, morepreferably from about 1.5 to about 5 N/15mm This is measured by the ASTMF-904 method. The bond strength is a physical measure of the adhesiveforce between the layers. It is related to the two layers of a film withthe lowest bond strength between two layers of the same film. Theadhesive strengths set as contemplated herein result in a favorablemechanical stability over the storage time of the packaged cosmeticproduct.

Also, the strength between two bonded (sealed or sealed-off) filmsshould be sufficient. According to a preferred embodiment of the presentdisclosure, the seal strength of the packaging (VP) is from about 10 toabout 40 N/15mm, preferably from about 15 to about 35 N/15mm, morepreferably from about 20 to about 30 N/15mm, under the conditions ofabout 150° C., about 2.54 cm (1″) and about 4 kg/cm2. The seal strengthis measured according to ASTM F-88 under the above conditions. Thechallenge with packaging is always to ensure the mechanical durabilityof the packaging while at the same time making the contents easilyaccessible to the user. Adjusting the seal strength to these valuesenables both of these objectives to be achieved.

The term sealed seam refers to a seam by which the package is closed.Usually, two films are placed on top of each other for closing thepackage and are pressed together by a force perpendicular to the filmsurface. By heating the films in the area that is being compressed,parts of the compressed areas may fuse together, so that the films arewelded together. There may also be an adhesive between the compressedfilms that strengthens the seam.

The product as contemplated herein comprises as a second component acosmetic composition (KM) which is packaged in the packaging (VP) andcontains at least one oxidizing agent and a thickening agent from thegroup of xanthanes.

The intended use of the product as contemplated herein is oxidativecolor change. For this purpose—as already described above—a cosmeticcomposition (KM) containing an oxidizing agent is usually mixed with asecond composition (B) which is prepared separately from (KM). In thisway, the ready-to-use oxidative color changing agent is produced.Depending on whether the oxidative color change is intended to achieve ableaching, brightening or coloring effect, the composition (B) maycontain different ingredients. If pure lightening or bleaching is to beachieved, composition (B) contains at least one alkalizing agent. Ifoxidative coloration is desired, the composition (B) often contains theoxidative colorant precursors in addition to the alkalizing agent. Inorder to ensure that the compositions (KM) and (B) may be mixedsufficiently quickly, both the composition (KM) and the composition (B)are usually free-flowing, aqueous or water-containing compositions.

As contemplated herein, the composition (KM) is an aqueous composition.The water content of the composition (KM) may, for example, be fromabout 60 to about 97% by weight, preferably from about 75 to about 93%by weight, more preferably from about 78 to about 91% by weight, inparticular from about 80 to about 88.0% by weight, based on the totalweight of the composition (KM). All weight data in % by weight refer tothe total weight of water contained in the composition (KM), which isset in relation to the total weight of the composition (KM).

The cosmetic composition (KM) contains as first essential ingredient a)at least one oxidizing agent. Preference is given to certain oxidizingagents. It is therefore advantageous in the context of the presentdisclosure if the cosmetic composition (KM) contains at least oneoxidizing compound selected from the group of persulfates, chlorites,hydrogen peroxides and attachment products of hydrogen peroxides tourea, melamine and sodium borate, in particular hydrogen peroxides. Ascontemplated herein, the use of hydrogen peroxide has proven to beparticularly advantageous.

The concentration of the oxidizing agent in the composition (KM) isdetermined on the one hand by the legal requirements and on the otherhand by the desired effect; preferably from about 0.5 to about 20.0% byweight solutions in water are used. Therefore, it is found to bepreferred if the cosmetic composition (KM) contains at least oneoxidizing compound, in particular hydrogen peroxide, in a total amountof from about 0.1 to about 10% by weight, preferably from about 0.2 toabout 8.0% by weight, preferably from 0.2 to 7.0% by weight, inparticular from about 0.2 to about 6.0% by weight, based on the totalweight of the cosmetic composition (KM). The higher the content ofoxidizing agent, in particular hydrogen peroxide, in the composition(KM), the greater is the amount of gas produced in the case of aproportional decomposition of the oxidizing agent. Compositionscontaining a higher concentration of oxidizing agent are therefore muchmore difficult to package in packaging (VP) than compositions containinga lower concentration of oxidizing agent. The amount of hydrogenperoxide refers to about 100% hydrogen peroxide.

In the course of the work leading to this present disclosure, it wasfound that the product as contemplated herein is particularly suitablefor the packaging and stable storage of higher concentrated hydrogenperoxide compositions (KM). Thus, packaging (VP) as contemplated herein,which contained compositions (KM) with from about 9 to about 12% byweight of hydrogen peroxide, showed no changes in volume (i.e. noswelling) and no unplanned openings (i.e. the packages did not burstopen) even after storage at elevated temperature for several weeks.

The cosmetic composition (KM) contains as the second essentialingredient b) at least one thickening agent from the group of xanthanes.The use of xanthanes has proved to be particularly advantageous sincethey ensure sufficient thickening over a long period of time even underhighly acidic conditions and in the presence of an oxidizing agent. Thethickening ensures a good handling of the cosmetic composition (KM). Inorder to ensure sufficient thickening, at least one thickening agent ispreferably used in certain quantity ranges. It is therefore advantageousin the context of the present disclosure if the cosmetic composition(KM) contains the at least one thickening agent selected from the groupof xanthanes in a total amount of from about 0.1 to about 10% by weight,preferably of from about 0.2 to about 8.0% by weight, more preferably offrom about 0.2 to about 7.0% by weight, in particular of from about 0.2to about 6.0% by weight, based on the total weight of the cosmeticcomposition (KM). In the context of the present disclosure, the use ofxanthanes, which have an average particle diameter D50 of from about 140to about 200 μm and a viscosity (about 0.3% by weight solution in about0.3% KCl) of from about 250 to about 800 mPa·s (measured with Brookfieldviscometer at about 3 rpm), has proved useful. Such xanthanes arecommercially available under the trade name Keltrol CG-SFT from CPKelco, for example.

In the course of the work leading to this present disclosure, it hasbeen found that by using the aforementioned special thickening agent,the cosmetic composition (KM), which contains at least one oxidizingagent, may be packaged and stored in the special packaging (VP) withoutthis packaging—which has a barrier layer with a passage barrier effectfor gases and water vapour—expanding or bursting.

In this context, a very specific combination of oxidizing agent andthickening agent has proven to be advantageous. The product ascontemplated herein is therefore exemplifiedin a preferred embodiment inthat the cosmetic composition (KM) contains hydrogen peroxide as well asxanthane.

For further optimization of the storage stability, the above mentionedcompounds are preferably used in certain quantity ranges in thecomposition (KM). Particularly preferred embodiments are exemplified inthat the cosmetic composition (KM) comprises

-   -   a) from about 1.5 to about 15% by weight of hydrogen peroxide        and    -   b) from about 0.2 to about 6.0% by weight of xanthane, each        based on the total weight of the cosmetic product (KM).

The cosmetic composition (KM) preferably has an acidic pH value in orderto avoid or reduce decomposition of the oxidizing agent used, inparticular the hydrogen peroxide. It is therefore preferred in thecontext of the present disclosure that the cosmetic composition (KM) hasa pH value (measured at about 20° C.) of from about pH 1.5 to about pH5.0, preferably of from about pH 2.0 to about pH 4.7, more preferably offrom about pH 2.3 to about pH 4.4, in particular of from about pH 2.5 toabout pH 4.

The composition (KM) contained in the packaging (VP) contains theessential ingredients in an aqueous or aqueous-alcoholic carrier, whichmay be a cream, an emulsion, a gel or a surfactant-containing foamingsolution. In order to achieve the desired properties of these dosageforms, the composition (KM) may also contain additional activeingredients, auxiliary substances and additives.

The composition (KM) may also contain one or more acids to stabilize theoxidizing agent used, especially the hydrogen peroxide. It is thereforepreferred in the context of the present disclosure if the cosmeticcomposition (KM) additionally contains at least one acid selected fromthe group of dipicolin acid, lemon acid, vinegar acid, apple acid, milkacid, wine acid, salt acid, phosphorus acid, pyrophosphor acid and theirsalts, benzoe acid and salts thereof, 1-hydroxyethane-1,1-diphosphonicacid, ethylenediaminetetraacetic acid and salts thereof, sulfuric acidand mixtures, in particular a mixture of dipicolin acid, disodiumpyrophosphate, ethylenediaminetetraacetic acid and salts thereof and1-hydroxyethane-1,1-diphosphonic acid.

A particularly high stabilization of the oxidizing agent, in particularof the hydrogen peroxide, is achieved if the above-mentioned acids areused in specific amounts. It is therefore advantageous in this contextif the at least one acid, in particular the mixture of dipicolin acid,disodium pyrophosphate, ethylenediaminetetraacetic acid and its saltsand 1-hydroxyethane-1,1-diphosphonic acid, is contained in a totalamount of from about 0.1 to about 3.0% by weight, preferably of fromabout 0.5 to about 2.5% by weight, more preferably of from about 0.8 toabout 2.0% by weight, in particular of from about 0.9 to about 1.5% byweight, based on the total weight of the cosmetic composition (KM)

The following tables show particularly preferred forms AF 1 to AF 16 ofthe cosmetic composition (KM) contained in the packaging (VP) (allfigures in % by weight, unless otherwise indicated).

AF 1 AF 2 AF 3 AF 4 Oxidizing agent 0.5-20 1.0-18  1.2-16  1.5-15 Xanthane 0.1-10 0.2-8.0 0.2-7.0 0.2-6.0 Cosmetic carrier ¹⁾ ad 100 ad100 ad 100 ad 100

AF 5 AF 6 AF 7 AF 8 Oxidizing agent ²⁾ 0.5-20 1.0-18  1.2-16  1.5-15 Xanthane 0.1-10 0.2-8.0 0.2-7.0 0.2-6.0 Cosmetic carrier ¹⁾ ad 100 ad100 ad 100 ad 100

AF 9 AF 10 AF 11 AF 12 Oxidizing agent ²⁾ 0.5-20 1.0-18 1.2-16  1.5-15 Xanthane 0.1-10  0.2-8.0 0.2-7.0 0.2-6.0 Acid  0.1-3.0 0.50-2.5  0.8-2.00.9-1.5 Cosmetic carrier ¹⁾ ad 100 ad 100 ad 100 ad 100

AF 13 AF 14 AF 15 AF 16 Oxidizing agent ²⁾ 0.5-20 1.0-18 1.2-16  1.5-15 Xanthane 0.1-10  0.2-8.0 0.2-7.0 0.2-6.0 Acid ³⁾  0.1-3.0 0.50-2.5 0.8-2.0 0.9-1.5 Cosmetic carrier ¹⁾ ad 100 ad 100 ad 100 ad 100 ¹⁾Aqueous or aqueous-alcoholic carrier ²⁾ Hydrogen peroxide, amountcalculated on about 100% hydrogen peroxide, ³⁾ Selected from a mixtureof dipicolin acid, disodium pyrophosphate and1-hydroxyethane-1,1-diphosphonic acid.

The previously described embodiments AF 1 to 16 are each packaged inpackaging (VP) with the following layout of the multi-layer film (F)(from interior (in contact with the cosmetic composition (KM)) toexterior):

-   -   a) *Interior*-Layer (P1)-Layer (P2)-Barrier layer        (BS)-*Exterior*,    -   b) *Interior*-Layer (P1)-Barrier layer (BS)-Layer        (P2)-*Exterior*,    -   c) *Interior*-Layer (P2)-Layer (P1)-Barrier layer        (BS)-*Exterior*,    -   d) *Interior*-Layer (P2)-Barrier layer (BS)-Layer        (P1)-*Exterior*,    -   e) *Interior*-Barrier layer (BS)-Layer (P1)-Layer        (P2)-*Exterior*,    -   f) *Interior*-Barrier layer (BS)-Layer (P2)-Layer        (P1)-*Exterior*,    -   g) *Interior*-Layer (P1)-Frst adhesive layer (SK1)-Layer        (P2)-Second adhesive layer (SK2)-Barrier layer (BS)-*Exterior*,    -   h) *Interior*-Layer (P1)-Adhesive layer (SK1)-Layer (P2)-Barrier        layer (BS)-*Exterior*,    -   i) *Interior*-Layer (P1)-Layer (P2)-Second adhesive layer        (SK2)-Barrier layer (BS)-*Exterior*,    -   j) *Interior*-Barrier layer (BS)-First adhesive layer        (SK1)-Layer (P1)-Second adhesive layer (SK2)-Layer        (P2)-*Exterior*,    -   k) *Interior*-Barrier layer (BS)-Adhesive layer (SK)-Layer        (P1)-Layer (P2)-*Exterior*,    -   l) *Interior*-Barrier layer (BS)-Layer (51)-Adhesive layer        (SK)-Layer (P2)-*Exterior*,    -   m) *Interior*-Layer (P1)-First adhesive layer (SK1)-Barrier        layer (BS)-Second adhesive layer (SK2)-Layer (P2)-*Exterior*,    -   n) *Interior*-Layer (P1)-Adhesive layer (SK)-Barrier layer        (BS)-Layer (P2)-*Exterior*,    -   o) *Interior*-Layer (P1)-Barriere Layer (BS)-Adhesive layer        (SK)-Layer (P2)-*Exterior*.

The products obtained in this way have a high storage stability and awater loss during storage that is within an acceptable range. Noswelling or delamination of the packaging (VP) during storage of thesecosmetic products as contemplated herein was observed.

The product as contemplated herein is used for the purpose of oxidativecolor change. For this purpose, the composition (KM) packaged in thepackaging (VP), which is the oxidizing agent composition, is mixed withat least one further composition (B) to produce the ready-to-use colorchanging agent. To prevent incompatibilities or premature reaction, thecompositions (KM) and (B) are packaged separately.

A particularly preferred product as contemplated herein is exemplied inthat it comprises a composition (B) separately prepared from composition(KM), wherein composition (B) contains at least one compound selectedfrom oxidative colorant precursor, direct dyes, alkalizing agents andmixtures thereof. Preferred products of the present disclosureadditionally comprises at least one second cosmetic composition (KM2)which contains at least one compound selected from oxidative colorantprecursor, direct dyes, alkalizing agents and mixtures thereof and whichis packaged separately from the cosmetic composition (KM).

If oxidative coloration is desired, composition (B) contains at leastone oxidative colorant precursor. Oxidative colorant precursors may bedivided into developers and couplers, whereby the developers are usuallyused in the form of their physiologically compatible salts (e.g. in theform of their hydrochlorides, hydrobromides, hydrogen sulfates orsulfates) due to their greater sensitivity to oxygen. Coupler componentsalone do not form a significant coloration in the course of oxidativecoloration, but always require the presence of developer components.Preferably such agents contain at least one oxidative colorant precursorof the developer type and at least one oxidative colorant precursor ofthe coupler type. Particularly suitable oxidative colorant precursors ofthe developer type are selected from at least one compound from thegroup formed by p-phenylenediamine, p-toluenediamine,2-(2-hydroxyethyl)-p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-methoxymethyl-p-phenylenediamine,N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amineN,N′-bis-(2-hydroxyethyl)-N,N′-bis-(4-aminophenyl)-1,3-diamino-propan-2-ol,bis-(2-hydroxy-5-aminophenyl)methane,1,3-bis-(2,5-diaminophenoxy)propane-2-ol,N,N′-bis-(4-aminophenyl)-1,4-diazacycloheptane,1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane p-Aminophenol,4-amino-3-methylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(1,2-dihydroxyethyl)phenol,4-amino-2-(diethylaminomethyl)phenol4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5 ,6-tetraamino-pyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triamino-pyrimidine,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-on and theirphysiologically compatible salts.

Particularly suitable oxidative colorant precursors of the coupler typeare selected from the group formed by 3-aminophenol,5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol,2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol,5-(2-hydroxyethyl)-amino-2-methylphenol, 2,4-dichloro-3-aminophenol,2-aminophenol, 3-phenylene-diamine, 2-(2,4-diaminophenoxy)ethanol,1,3-bis(2,4-diaminophenoxy)propane,1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene, 1,3-bis(2,4-diaminophenyl)propane,2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, 2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol,2-({3-[2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,2-({3-[2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol,2-[3-morpholin-4-ylphenyl)amino]ethanol,3-amino-4-(2-methoxy-ethoxy)-5-methylphenylamine,1-amino-3-bis-(2-hydroxyethyl)aminobenzene, resorcinol,2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene,2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine,1-phenyl-3-methylpyrazol-5-on, 1-naphthol, 1,5-dihydroxy-naphthalene,2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,1,8-dihydroxy-naphthalene, 4-hydroxy-indole, 6-hydroxyindole,7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindolineor mixtures of these compounds or their physiologically acceptablesalts.

In addition, the composition (B) may also contain one or more directdyes. Suitable non-ionic direct dyes may be selected from the group HCYellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, DisperseBlue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, DisperseBlack 9, 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,1,4-bis(2-hydroxyethyl)-amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)aminophenol,2-(2-hydroxyethyl)amino-4,6-dinitro-phenol, 4-[(2-hydroxyethyl) amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,4-[(3-hydroxypropyl)amino]-3 -nitrophenol, 4-nitro-o-phenylenediamine,6-nitro-1,2,3,4-tetrahydroquinone, 2-hydroxy-1,4-naphthoquinone,picramine acid and its salts, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoe acid and 2-chloro-6-ethylamino-4-nitrophenol.

Suitable anionic direct dyes may be selected from the group of AcidYellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, AcidRed 33, Acid Red 52, Pigment Red 57:1, Acid Blue 7, Acid Green 50, AcidViolet 43, Acid Black 1, Acid Black 52, Bromophenol Blue andTetrabromophenol Blue.

Suitable cationic direct dyes are cationic triphenylmethane dyes, suchas Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,aromatic systems substituted with a quaternary nitrogen group, such asBasic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and BasicBrown 17, cationic anthraquinone dyes, such as HC Blue 16 (Bluequat B),and direct dyes containing a heterocycle containing at least onequaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31and Basic Red 51. The cationic direct dyes marketed under the trademarkArianor are also suitable cationic direct dyes as contemplated herein.

Dyeing processes on keratinous fibers are usually carried out in analkaline environment. In order to protect the keratinous fibers and alsothe skin as much as possible, however, the adjustment of a too high pHvalue is not desirable. Therefore, it is preferable if the pH value ofcomposition (B) is between about 7 and about 11, especially betweenabout 8 and about 10.5. For the purposes of the present disclosure, thepH values are pH values measured at a temperature of about 22° C.

Composition (B) may contain at least one alkalizing agent. Thealkalizing agents usable for adjusting the preferred pH value ascontemplated herein may be selected from the group formed by ammonia,alkanolamines, basic amino acids, and inorganic alkalizing agents suchas (earth) alkali metal hydroxides, (earth) alkali metal metasilicates,(earth) alkali metal phosphates and (earth) alkali metal hydrogenphosphates. Preferred inorganic alkalizing agents are magnesiumcarbonate, sodium hydroxide, potassium hydroxide, sodium silicate andsodium metasilicate. Organic alkalizing agents which can be used ascontemplated herein are preferably selected from monoethanolamine,2-amino-2-methyl-propanol and triethanolamine The basic amino acidsusable as alkalizing agents as contemplated herein are preferablyselected from the group formed from arginine, lysine, ornithine andhistidine, especially preferably arginine. However, in the course of theinvestigations into the present disclosure, it was found that furtheragents as contemplated herein additionally contain an organic alkalizingagent. An embodiment of the present disclosure is exemplified in thatthe agent additionally contains at least one alkalizing agent selectedfrom the group formed by ammonia, alkanolamines and basic amino acids,in particular ammonia, monoethanolamine and arginine or its compatiblesalts.

The composition (B) may further contain additional active ingredients,auxiliary substances and additives. For example, one or more fatcomponents from the group of C₁₂-C₃₀ fatty alcohols, C₁₂-C₃₀ fatty acidtriglycerides, C₁₂-C₃₀ fatty acid monoglycerides, C₁₂-C₃₀ fatty aciddiglycerides and/or hydrocarbons may be included.

Preferably, a surface-active substance may be added to composition (B),whereby such surface-active substances are referred to as surfactants oremulsifiers, depending on the area of application: they are preferablyselected from anionic, zwitterionic, amphoteric and non-ionicsurfactants and emulsifiers.

The composition (B) preferably contains at least one anionic surfactant.Preferred anionic surfactants are fatty acides, alkyl sulfates, alkylether sulfates and ether carbon acids with 10 to 20 carbon atoms in thealkyl group and up to 16 glycol ether groups in the molecule.

Furthermore, composition (B) may additionally contain at least onezwitterionic surfactant. Preferred zwitterionic surfactants arebetaines, N-alkyl-N,N-dimethylammonium-glycinate,N-acyl-aminopropyl-N,N-dimethylammoniumglycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines. A preferredzwitterionic surfactant is known under the INCI designationCocamidopropyl Betaine.

Furthermore, it may be intended that the composition (B) contains atleast one amphoteric surfactant. Preferred amphoteric surfactants areN-alkyl glycines, N-alkyl propionic acids, N-alkyl-amino butter acids,N-alkyl amino dipropion acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkyl amino propionic acids and alkyl amino aceticacids. Particularly preferred amphoteric surfactants are N-coconutalkylaminopropionate, as coconut acylaminoethylamino propionate andC₁₂-C₁₈ acyl sarcosine.

Furthermore, it has proven to be advantageous if the composition (B)contains further, non-ionic surface-active substances. Preferrednon-ionic surfactants are alkyl polyglycoside and alkylene oxide plantproducts on fatty alcohols and fatty acids with 2 to 30 moles ofethylene oxide per mole of fatty alcohol or fatty acid. Compositionswith outstanding properties are also obtained if they contain fatty acidesters of ethoxylated glycerol as non-ionic surfactants.

The non-ionic, zwitterionic or amphoteric surfactants are used inproportions of from about 0.1 to about 45% by weight, preferably fromabout 1 to about 30% by weight and particularly preferably from about 1to about 15% by weight, based on the total weight of the composition(B).

Composition (B) may also contain at least one thickening agent. Thereare no restrictions in principle with regard to these thickening agents.Both organic and purely inorganic thickening agents may be used.Suitable thickening agents are anionic, synthetic polymers, cationic,synthetic polymers, naturally occurring thickening agents such asnon-ionic guar gums, scleroglucan gums or xanthane gums, gum arabicum,ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar-agar,carob bean gum, pectins, alginates, starch fractions and derivativessuch as amylose, amylo-pectin and dextrine, as well as cellulosederivatives such as methyl cellulose, carboxyalkyl celluloses andhydroxyalkyl celluloses, non-ionic, fully synthetic polymers such aspolyvinyl alcohol or polyvinyl pyrrolidinone as well as inorganicthickening agents, in particular phyllosilicates such as bentonite,especially smectites such as montmorillonite or hectorite.

Furthermore, composition (B) may contain other active ingredients,auxiliary substances and additives, such as non-ionic polymers such asvinyl pyrrolidine/vinyl acrylat copolymers, polyvinyl pyrrolidinone,vinyl pyrrolidine/vinyl acetate copolymers, polyethylene glycols andpoly-siloxanes; additional silicones such as volatile or non-volatile,straight-chain, branched or cyclic, crosslinked or non-crosslinkedpolyalkylsiloxanes (such as dimethicones or cyclomethicones),polyarylsiloxanes and/or polyalkylarylsiloxanes, in particularpolysiloxanes with organo-functional groups, such as substituted orunsubstituted amines (amodimethicones), carboxyl, alkoxy and/or hydroxylgroups (dimethicone copolyols), linearpolysiloxane(A)-polyoxyalkylene(B) block copolymers, grafted siliconepolymers; cationic polymers such as quaternized cellulose ethers,polysiloxanes with quaternary groups, dimethyldiallylammonium chloridepolymers, acrylamidedimethyldiallylammonium chloride copolymers,dimethylamino-ethyl methacrylate-vinylate vinyl pyrrolidinone copolymersquaternized with diethyl sulfate, vinyl pyrrolidinone-imidazoliummethochloride copolymers and quaternized polyvinyl alcohol; zwitterionicand amphoteric polymers; anionic polymers such as, for example,polyacrylacids or cross-linked polyacrylics; structurants such asglucose, maleic acid and lactic acid, hair-conditioning compounds suchas phospholipids, for example lecithin and cephalins; perfume oils,dimethyl iso-sorbide and cyclodextrins; fiber structure-improving activesubstances, in particular mono-, di- and oligo-saccharides such asglucose, galactose, fructose, fructose and lactose; dyes for colouringthe composition; anti-dandruff active substances such as piroctoneolamines, zinc omadine and climbazole; amino acids and oligopeptides;animal and/or vegetable-based protein hydrolysates, as well as in theform of their fatty acid condensation products or optionally anionicallyor cationically modified derivatives; fatty substances and vegetableoils; sunscreens and UV blockers; active ingredients such as panthenol,panthenic acid, pantolactone, allantoin, pyrrolidinone-carbon acid andits salts, and bisabolol; polyphenols, in particular hydroxyzimt acids,6,7-dihydroxycoumarins, hydroxybenzoeacids, catechins, tannins,leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols;ceramides or pseudoceramides; vitamins, provitamins and vitaminprecursors; plant extracts; fats and waxes such as fatty alcohols,beeswax, montan wax and paraffins; swelling and penetrating agents suchas glycerine, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas as well as primary, secondary and tertiaryphosphates; anti-caking agents such as latex, styrene/PVP andstyrene/acrylamide copolymers; pearlescent agents such as ethyleneglycol mono- and distearate as well as PEG-3 distearate and pigments.

The selection of these additional substances will be made by the expertaccording to the desired properties of the composition (B) as well asthe product as contemplated herein. With regard to further optionalcomponents and the quantities of these components used, explicitreference is made to the relevant handbooks known to the expert. Theadditional active ingredients and auxiliary substances are preferablyused in the composition (B) in quantities of from about 0.0001 to about25% by weight each, in particular from about 0.0005 to about 15% byweight, in each case based on the total weight of the composition (B).

The following examples explain the present disclosure without limitingit:

EXAMPLES

A 100 nm thick layer of aluminum was vapor-deposited onto a film layerof biaxially oriented polypropylene with a thickness of 12 μm(micrometer). The aluminum layer was then painted over with approx. 3g/m² of ORMOCER polymer and cured. A 70 μm (micrometer) thick layer ofpolyethylene was then applied to the ORMOCER layer. A packaging (VP) wasproduced from the film. The film is also provided with a PET layer 20 μmthick.

The packaging (VP) was filled with the following composition (KM1) (allfigures in % by weight). The oxidizing agent is preferably hydrogenperoxide.

Ingredients KM1 Potassium hydroxide (50%) 0.66 Dipicolin acid 0.10Disodium pyrophosphate 0.030 1-hydroxyethan-1,1-diphosphon acid (60%)1.5 Keltrol CG-SFT (xanthane) 2.0 H₂O₂ 50% (oxidizing agent) 8.21,2-propanediol 4.0 Water ad 100

The cosmetic composition KM1 was filled into the packaging (VP)described above. The packaging was then stored at 40° C. for 24 weeks.The packages were not inflated or delaminated.

While at least one exemplary embodiment has been presented in theforegoing detailed description, it should be appreciated that a vastnumber of variations exist. It should also be appreciated that theexemplary embodiment or exemplary embodiments are only examples, and arenot intended to limit the scope, applicability, or configuration of thevarious embodiments in any way. Rather, the foregoing detaileddescription will provide those skilled in the art with a convenient roadmap for implementing an exemplary embodiment as contemplated herein. Itbeing understood that various changes may be made in the function andarrangement of elements described in an exemplary embodiment withoutdeparting from the scope of the various embodiments as set forth in theappended claims.

The invention claimed is:
 1. Cosmetic product for modifying the naturalcolor of keratinous fibers, comprising (i) at least one packagingcomprising at least one multi-layer film comprising at least one firstpolymer layer, at least one second polymer layer and at least onebarrier layer, and (ii) at least one cosmetic composition packaged andincluded in the packaging: a) at least one oxidizing compound and b) atleast one thickening agent, selected from the group of xanthanes,wherein the first polymer layer is formed of polyethylene terephthalateor polyethylene naphthalate; the second polymer layer is formed of apolyolefin; and the barrier layer is formed of metallized orientedpolypropylene.
 2. Cosmetic product according to claim 1, wherein thefirst polymer layer has a layer thickness of from about 4 μm to about 50μm; the second polymer layer has a layer thickness of from about 20 μmto about 150 μm; and/or the layer thickness of the barrier layer is fromabout 4 μm to about 20 μm.
 3. Cosmetic product according to claim 1,wherein the multi-layer film has an Oxygen Transmission Rate at about23° C. and about 50% relative humidity of from about 0.1 to about 5cc/m²/d/bar and has a water vapor permeability at about 38° C. and about100% relative humidity of from about 0.1 to about 5 g/m² d.
 4. Cosmeticproduct according to claim 1, wherein the film has an adhesive strengthof from about 0.1 to about 10 N/15 mm.
 5. Cosmetic product according toclaim 1, wherein the packaging has a seal strength of from about 10 toabout 40 N/15 mm under the conditions of about 150° C., about 2.54 cm(1″) and about 4 kg/cm².
 6. Cosmetic product according to claim 1,wherein the at least one multi-layer film comprises the at least onebarrier layer between the at least one first polymer layer and the atleast one second polymer layer.
 7. Cosmetic product according to claim1, wherein the first polymer layer forms the outer layer.
 8. Cosmeticproduct according to claim 1, wherein the cosmetic composition comprisesat least one oxidizing compound, in a total amount of from about 0.5 toabout 20% by weight, relative to the total weight of the cosmeticcomposition.
 9. Cosmetic product according to claim 1, wherein thecosmetic composition has a pH value (measured at about 20° C.) of aboutpH 1.5 to about pH 5.0.
 10. Cosmetic product according to claim 1,wherein the cosmetic composition comprises at least one thickening agentchosen from the group of xanthanes in a total amount of from about 0.1to about 10% by weight, relative to the total weight of the cosmeticcomposition.
 11. Cosmetic product according to claim 1, wherein thefirst polymer layer has a layer thickness of from about 6 μm to about 20μm; the second polymer layer has a layer thickness of from about 40 μmto about 90 μm; and/or the layer thickness of the barrier layer is fromabout 6 μm to about 15 μm.
 12. Cosmetic product according to claim 11,wherein the multi-layer film has an Oxygen Transmission Rate at about23° C. and about 50% relative humidity of from about 0.5 to about 2.5cc/m²/d/bar and has a water vapor permeability at about 38° C. and about100% relative humidity of from about 0.5 to about 2.5 g/m² d. 13.Cosmetic product according to claim 1, wherein the multi-layer film hasan Oxygen Transmission Rate at about 23° C. and about 50% relativehumidity of from about 0.5 to about 2.5 cc/m²/d/bar and has a watervapor permeability at about 38° C. and about 100% relative humidity offrom about 0.5 to about 2.5 g/m² d.
 14. Cosmetic product according toclaim 1, wherein the film has an adhesive strength of from about 1.5 toabout 5 N/15mm.
 15. Cosmetic product according to claim 1, wherein thepackaging has a seal strength from about 20 to about 30 N/15mm under theconditions of about 150° C., about 2.54 cm (1″) and about 4 kg/cm². 16.Cosmetic product according to claim 1, wherein the cosmetic compositioncomprises at least one oxidizing compound in a total amount of fromabout 1.5 to about 15% by weight relative to the total weight of thecosmetic composition.
 17. Cosmetic product according to claim 1, whereinthe cosmetic composition has a pH value (measured at about 20° C.) ofabout pH 2.5 to about pH
 4. 18. Cosmetic product according to claim 1,wherein the first polymer layer is formed of polyethylene terephthalateand the second polymer layer (P2) is formed of polyethylene; the firstpolymer layer has a layer thickness of from about 6 μm to about 20 μm;the second polymer layer has a layer thickness of from about 40 μm toabout 90 μm; and/or the layer thickness of the barrier layer is fromabout 6 μm to about 15 μm; the multi-layer film has an OxygenTransmission Rate at about 23° C. and about 50% relative humidity offrom about 0.5 to about 2.5 cc/m²/d/bar and has a water vaporpermeability at about 38° C. and about 100% relative humidity of fromabout 0.5 to about 2.5 g/m² d; the film has a adhesive strength of fromabout 1.5 to about 5 N/15 mm; the packaging has a seal strength of fromabout 20 to about 30 N/15 mm under the conditions about 150° C., about2.54 cm (1″) and about 4 kg/cm²; the at least one multi-layer filmcomprises the at least one barrier layer between the at least one firstpolymer layer and the at least one second polymer layer; the firstpolymer layer forms the outer layer; the cosmetic composition compriseshydrogen peroxide in a total amount of from about 1.5 to about 15% byweight relative to the total weight of the cosmetic composition; thecosmetic composition has a pH value (measured at about 20° C.) of aboutpH 2.5 to about pH 4; and the cosmetic composition comprises at leastone thickening agent chosen from the group of xanthanes in a totalamount of from about 0.2 to about 6% by weight relative to the totalweight of the cosmetic composition.